IOP Conference Series: Earth and Environmental Science

PAPER • OPEN ACCESS You may also like

- Reduction in urban water use leads to less
Review on Physicochemical, Chemical, and wastewater and fewer emissions:analysis
of three representative U.S. cities
Biological Processes for Pharmaceutical Aysegul Petek Gursel, Camille Chaudron,
Ioanna Kavvada et al.

Wastewater - Review in recent researches and

applications of technology of
environmental microbiology metagenomics
To cite this article: Zhenchen Li and Ping Yang 2018 IOP Conf. Ser.: Earth Environ. Sci. 113 012185 in water treatment engineering
Q Li, H You, W Xie et al.

- Effect of Sorting by a Hydrocyclone on

Denitrification Performance of Activated
Sludge
View the article online for updates and enhancements. Jiaping Xu and Hualin Wang

This content was downloaded from IP address 81.91.136.138 on 06/12/2021 at 12:02

ICAESEE 2017 IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
113 (2018) 012185 doi:10.1088/1755-1315/113/1/012185

Review on Physicochemical, Chemical, and Biological

Processes for Pharmaceutical Wastewater

Zhenchen Li, Ping Yang*

School of Architecture and Environment, Sichuan University, Chengdu 610065, China
* Corresponding author E-mail: yping63@163.com

Abstract. Due to the needs of human life and health, pharmaceutical industry has made great
progress in recent years, but it has also brought about severe environmental problems. The
presence of pharmaceuticals in natural waters which might pose potential harm to the ecosystems
and humans raised increasing concern worldwide. Pharmaceuticals cannot be effectively
removed by conventional wastewater treatment plants (WWTPs) owing to the complex
composition, high concentration of organic contaminants, high salinity and biological toxicity of
pharmaceutical wastewater. Therefore, the development of efficient methods is needed to
improve the removal effect of pharmaceuticals. This review provides an overview on three types
of treatment technologies including physicochemical, chemical and biological processes and
their advantages and disadvantages respectively. In addition, the future perspectives of
pharmaceutical wastewater treatment are given.

1. Introduction
Pharmaceutical industry has been developed so rapidly in the past few decades that a large amount of
pharmaceuticals is being used in many fields such as agriculture, poultry farming, fishery and human
health [1]. Pharmaceuticals can be divided into three categories according to their production methods:
extraction pharmacy, biopharmacy and chemical pharmacy [2]. Among them, chemical pharmacy is the
main trend at present [3]. Although the use of pharmaceuticals has brought people a lot of benefits, also
caused great harm to the environment due to its structural stability and non-biodegradation [4].
Pharmaceuticals as an emerging contaminant have been reported to be present in different
environmental compartment such as soil, surface waters or even in drinking water [5], which might
potentially cause negative effects on the environment and the human health [6]. A large amount of water
is consumed due to the requirement of the pharmaceutical process, at the same time, some harmful drugs
are secreted in the process and then merge with the water [7], resulting in a great production of
wastewater, which has arisen the global occurrence of pharmaceuticals in aquatic solution as a serious
problem. The main characteristics of pharmaceutical wastewater are as follows: (a) high concentration
of organic contaminants, large concentration fluctuation and complex composition [8]; (b) high BOD
value and COD value and large difference of BOD/COD value in wastewater [9]; (c) high NH3-N
concentration and chroma [10]; (d) high suspended solids concentration and salinity [11]. Therefore,
pharmaceutical wastewater is difficult to be treated by wastewater treatment plants (WWTPs) which use
conventional physicochemical and biological treatments. In this paper, three types of technologies
including physicochemical, chemical and biological treatment for pharmaceutical wastewater are
reviewed, aiming to offer a brief introduction of treatment of this refractory industrial effluent.

2. Technologies for pharmaceutical wastewater

Content from this work may be used under the terms of the Creative Commons Attribution 3.0 licence. Any further distribution
of this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI.
Published under licence by IOP Publishing Ltd 1
ICAESEE 2017 IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
113 (2018) 012185 doi:10.1088/1755-1315/113/1/012185

2.1 Physicochemical processes

2.1.1 Coagulative precipitation Coagulation precipitation technology is currently widely used at home
and abroad, because of its economic reliability which is the first choice of physical-chemical treatment
technologies due to its economy reliability. Under the effect of charge neutralisation, bridging and
netting by adding chemical agents [12], the stability of the colloids in wastewater is destroyed, resulting
in colloidal coalescence, bonding, and precipitation under the action of gravity, thereby being separated
from wastewater. Coagulants in common are divided into two categories: a. inorganic salt coagulant,
mainly aluminum (aluminum sulfate, alum, etc.) and iron salts (ferric chloride, ferrous sulfate and ferric
sulfate, etc.) b. polymer coagulants which can be divided into inorganics (PAC, PFS, etc.) and organics
(polyacrylamide, etc.). By adding coagulants, it can not only play a role of adsorption and flocculation
in wastewater, but also improve the biodegradability. However, this process has a low removal rate of
dissolved substances and generates a large amount of chemical sludge, meanwhile, it is difficult to
completely remove pathogens and toxic trace substances in wastewater. Therefore, it is often used as a
pretreatment in sewage treatment.

2.1.2 Flotation Flotation process is an effective solid - liquid and liquid - liquid separation method,
through accessing to a large number of micro-bubbles in the water to make it adhere to the concentration
of similar pollutants in the wastewater, thereby floating to the water surface, so as to achieve the purpose
of separation and removal of pollutants [13]. According to different ways to produce micro-bubbles,
flotation process can be divided into the electro-flotation, induced air flotation and dissolved air flotation.
Flotation process is commonly used for the separation of small particles whose density is close to or
smaller than that of water, with the advantage of less investment, low energy consumption, simple
process, easy maintenance and so on.

2.1.3 Membrane separation Membrane separation process is a method, including diffusion-dialysis,

electrodialysis, reverse osmosis and ultrafiltration, which utilizes outside energy or chemical potential
difference as a driving force to separate contaminants from wastewater [14]. Membrane separation can
deal with wastewater that is difficult to be treated by traditional methods, and the change of water quality
will not have a great impact on the treatment effect. This method has the advantages of simple process,
convenient operation and no change of the nature of the sewage, but at present, it is a problem that the
membrane module is expensive and prone to being polluted.

2.1.4 Adsorption Adsorption process is a method which utilizes porous solids (activated carbon, silica
gel, artificial pumice and so on) to adsorb contaminants in wastewater so as to recover or remove
contaminants, thus purifying wastewater [15]. Adsorption can reduce the concentration of refractory
organic matter in wastewater, improve biochemical and recover useful ingredients, however, the cost of
adsorbent is high, and the regeneration of adsorbent needs a further study.

2.1.5 Electrolysis By applying an electric current, an array of chemical reactions will happen to change
the property and structure of organic pollutants in wastewater. The contaminants in wastewater can be
oxidized and reduced by the hydrogen and oxygen produced at the two level of the electrode. In
electrolysis, there is a variety of mechanisms, the electrochemical role which is the most important,
coupled with flotation and flocculation, so as to remove contaminants in wastewater under their
respective functions [16]. Electrolysis process has the advantages of simple operation and management,
stable effluent quality, impressed decolorization effect and less area-covering. But the processing cost
is high due to the high energy consumption.

2.2 Chemical processes

2.2.1 Fe-C Fe-C process, ferric-carbon micro-electrolysis technology, is also known as iron reduction

2
ICAESEE 2017 IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
113 (2018) 012185 doi:10.1088/1755-1315/113/1/012185

method, zero-valent method. The method generally uses cast iron scrap and activated carbon or coke as
the electrolytic material and causes electric erosion under acidic conditions to form a plurality of fine
galvanic cells in the iron filings and between the iron filings and the carbon powder, so as to generate a
sufficient amount of active hydrogen, whose strong reducibility is able to decompose macromolecule
organic matter. At the same time, Fe(OH)3 flocs which have an adsorption effect are generated by Fe2+
under aeration conditions.
Therefore, Fe-C process is a method comprised of oxidation and reduction, adsorption, complexation
and electric flocculation, which can change the shape and structure of contaminants to remove refractory
substances, and improve biodegradability [17]. Its advantages are mainly simple process, low operating
costs and wide range of applications, but there may be iron sludge problems and the need for active
regeneration.

2.2.2 Fenton Fenton reagent is a combination of ferrous salt and hydrogen peroxide. Ferrous salt can
catalyze hydrogen peroxide to generate hydroxyl radicals (•OH) with extremely high oxidation potential
to oxidize organic compounds in wastewater. •OH with non-selectivity and extremely oxidizing ability
(E0=2.8eV) can degrade a variety of contaminants [9], therefore, Fenton process is suitable for treating
the wastewater of high concentration, hard-degradation and toxicity or as pretreatment before biological
treatment. Fenton oxidation has advantages of simple equipment, mild reaction conditions, easy
operation and the use of a wide range, however, there is a large amount of iron ions in effluent, which
needs follow-up treatment.

2.2.3 Ozonation Ozone is a strong oxidant with the redox potential of 2.07V, which has the highest
redox potential among commonly use chemical oxidants and strong disinfection and sterilization. There
are two oxidation mechanisms, namely direct reaction and indirect reaction. Direct reaction uses the
strong oxidation of ozone to directly oxidize pollutants. Indirect reaction means that ozone decomposes
in water to generate •OH with highly reactivity, thereby oxidizing contaminants in wastewater. On the
other hand, ozone has the function of open-loop and chain scission, which can make the macromolecular
organism become biodegradable small molecule organic substances, improving the biodegradability of
the wastewater [18]. Therefore, ozonation is especially suitable for the pretreatment of high
concentration, hardly biodegradable wastewater or the advanced treatment of the effluent of biological
treatment, which has good treatment effect on organic pollutants of high stability and refractory in
wastewater. The advantages of this method are fast rate, good effect, no secondary pollution and the less
remaining sludge.

2.2.4 Photocatalytic oxidation The n-type semiconductors such as TiO2, SrO2, WO3, SnO2 and so on,
are used as catalysts for photochemical degradation in photocatalytic oxidation process. When these
catalysts are irradiated by ultraviolet light, electron-hole pairs (h+-e-) will be formed and then migrate to
the semiconductor surface, resulting in a strong oxidation effect to generate •OH which can oxidize
contaminants in wastewater [19]. Photocatalytic oxidation process with its strong oxidizing power, no
secondary pollution and mild reaction conditions becomes an effective method of treating refractory
organic wastewater, which has a broader prospect, and the search for the photocatalyst of low cost and
strong stability is the main research direction.

2.3 Biological processes

2.3.1 SBR Sequencing batch reactor is completely mixed on flow pattern, which is a “water injection -
reaction - drainage” type of reactor. It is a kind of activated sludge sewage treatment technology operated
by intermittent aeration, consisting of five basic processes: injection, reaction, precipitation, drainage
and idleness. All the processes take turns in a reactor with aeration stirring device, therefore, there is no
need for a separate sedimentation tank [11]. The method has the advantages of simple process, flexible
operation, simple maintenance and management, strong compliance with impact resistance, stable

3
ICAESEE 2017 IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
113 (2018) 012185 doi:10.1088/1755-1315/113/1/012185

effluent quality, so it’s suitable for treating the wastewater with large fluctuations of water quality and
amount. However, SBR process takes a long time to carry out sludge settling and separation, and when
treating high-concentration wastewater, it is necessary to maintain high sludge concentration, lest high
viscosity bulking happened.

2.3.2 UASB Upflow anaerobic sludge bed process is an anaerobic biological treatment technology,
whose reactor is mainly composed of influent water distribution system, reaction zone, three-phase
separator, gas chamber and treated water discharge system. At the bottom of the reactor, there is a high
concentration of highly active sludge that converts most of the organic contaminants to CH4 and CO2
when the wastewater passes through the reactor from bottom to top. Due to the agitation of the digestive
gas and the adhesion of bubbles to the sludge, a sludge suspension layer is formed above the sludge
layer, which needs the three-phase separator to complete the separation of gas, liquid and solid phases
[20]. UASB reactor has the advantages of compact structure, large processing capacity, no mechanical
stirring, good treatment effect and low investment cost. However, it’s difficult in microbial
domestication and complex in management. In the initial stage of start-up, the intermittent pulse influent
needs to make up for the insufficient contact between the bacterial cells and the matrix caused by
insufficient gas production.

2.3.3 MBR Membrane bioreactor process is a combination of membrane technology and wastewater
biological treatment technology, which uses an ultrafiltration membrane instead of secondary
sedimentation tank to achieve sludge solid-liquid separation. As a sewage treatment technology
integrated with concentration and separation, MBR process can intercept activated sludge and
macromolecular organic contaminants by membrane separation device, overcoming the problem of
sludge expansion in the traditional activated sludge process. In addition, it can control hydraulic
retention time and sludge residence time flexibly, increase the concentration of activated sludge in the
aeration tank to improve the biological degradation rate and achieve automatic control. That not only
improve the removal efficiency of contaminants, but also make the effluent in many cases can be
recycled directly [21]. Membrane bioreactor has the advantages of strong microbial biomass interception
ability, high operation stability and high effluent quality. However, there are still some disadvantages
such as high cost, easy contamination of membrane module, limited membrane service life.

3. Conlusion
The pharmaceutical industry is one of the largest and prominent industries worldwide. At the same time,
the increasingly severe pollution caused by pharmaceutical wastewater highlights the need for a
sustainable treatment process. In this review, a number of treatment technologies and their advantages
and disadvantages were summarized. To reach the discharge standard, a combination of different
treatment technologies needs adopting. The conventional combed process usually decreases the
concentration of contaminants or recycle available components in wastewater, meanwhile improving
the biodegradability by physical or chemical pretreatment, and then the biological treatment is adopted
to further remove the contaminants in wastewater. On the other hand, future research should focus on
the treatment effect and the cost of these potential processes for pharmaceutical wastewater.

Acknowledgments
We would also like to thank the anonymous reviewers for their constructive comments on earlier
versions of the manuscript. This research is supported by the Sichuan science and technology support
program supported by Science and Technology Agency (Grant No.2015SZ0009). I am also thankful to
institution, which provided accurate date.

References
[1] Wang J, Wang S. Removal of pharmaceuticals and personal care products (PPCPs) from
wastewater: A review[J]. Journal of Environmental Management. 2016, 182: 620-640.

4
ICAESEE 2017 IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
113 (2018) 012185 doi:10.1088/1755-1315/113/1/012185

[2] Hubert P, Nguyen-Huu J J, Boulanger B, et al. Harmonization of strategies for the validation of
quantitative analytical procedures[J]. Journal of Pharmaceutical and Biomedical Analysis.
2004, 36(3): 579-586.
[3] Chen Z, Ren N, Wang A, et al. A novel application of TPAD–MBR system to the pilot treatment
of chemical synthesis-based pharmaceutical wastewater[J]. Water Research. 2008, 42(13):
3385-3392.
[4] Song J Y, Jhung S H. Adsorption of pharmaceuticals and personal care products over metal-
organic frameworks functionalized with hydroxyl groups: Quantitative analyses of H-bonding
in adsorption[J]. Chemical Engineering Journal. 2017, 322: 366-374.
[5] Li W C. Occurrence, sources, and fate of pharmaceuticals in aquatic environment and soil[J].
Environmental Pollution. 2014, 187: 193-201.
[6] Mirzaei A, Chen Z, Haghighat F, et al. Removal of pharmaceuticals and endocrine disrupting
compounds from water by zinc oxide-based photocatalytic degradation: A review[J].
Sustainable Cities and Society. 2016, 27: 407-418.
[7] Sophia A C, Lima E C, Allaudeen N, et al. Application of graphene based materials for
adsorption of pharmaceutical traces from water and wastewater- a review[J]. Desalination &
Water Treatment. 2016, 57(57): 1-14.
[8] Gago-Ferrero P, Gros M, Ahrens L, et al. Impact of on-site, small and large scale wastewater
treatment facilities on levels and fate of pharmaceuticals, personal care products, artificial
sweeteners, pesticides, and perfluoroalkyl substances in recipient waters[J]. Science of The
Total Environment. 2017, 601-602: 1289-1297.
[9] Segura Y, Martínez F, Melero J A. Effective pharmaceutical wastewater degradation by Fenton
oxidation with zero-valent iron[J]. Applied Catalysis B: Environmental. 2013, 136-137: 64-
69.
[10] Fazal S, Zhang B, Zhong Z, et al. Membrane Separation Technology on Pharmaceutical
Wastewater by Using MBR (Membrane Bioreactor)[J]. Journal of Environmental Protection.
2015, 06(04): 299-307.
[11] Shi X, Lefebvre O, Ng K K, et al. Sequential anaerobic–aerobic treatment of pharmaceutical
wastewater with high salinity[J]. Bioresource Technology. 2014, 153: 79-86.
[12] Yuan Y, Zhang H, Pan G. Flocculation of cyanobacterial cells using coal fly ash modified
chitosan[J]. Water Research. 2016, 97: 11-18.
[13] Suarez S, Lema J, Omil F. Pre-treatment of hospital wastewater by coagulation–flocculation
and flotation[J]. Bioresource Technology. 2009, 100(7): 2138-2146.
[14] Martínez F, López-Muñoz M J, Aguado J, et al. Coupling membrane separation and
photocatalytic oxidation processes for the degradation of pharmaceutical pollutants[J]. Water
Research. 2013, 47(15): 5647-5658.
[15] Putra E K, Pranowo R, Sunarso J, et al. Performance of activated carbon and bentonite for
adsorption of amoxicillin from wastewater: Mechanisms, isotherms and kinetics[J]. Water
Research. 2009, 43(9): 2419-2430.
[16] Ji Z. Electrochemical degradation of diclofenac for pharmaceutical wastewater treatment[J].
International Journal of Electrochemical Science. 2017: 7807-7816.
[17] Xu X, Cheng Y, Zhang T, et al. Treatment of pharmaceutical wastewater using interior micro-
electrolysis/Fenton oxidation-coagulation and biological degradation[J]. Chemosphere. 2016,
152: 23-30.
[18] Liu P, Zhang H, Feng Y, et al. Removal of trace antibiotics from wastewater: A systematic study
of nanofiltration combined with ozone-based advanced oxidation processes[J]. Chemical
Engineering Journal. 2014, 240: 211-220.
[19] Kanakaraju D, Glass B D, Oelgemöller M. Titanium dioxide photocatalysis for pharmaceutical
wastewater treatment[J]. Environmental Chemistry Letters. 2014, 12(1): 27-47.

5
ICAESEE 2017 IOP Publishing
IOP Conf. Series: Earth and Environmental Science1234567890
113 (2018) 012185 doi:10.1088/1755-1315/113/1/012185

[20] Alvarino T, Suarez S, Lema J M, et al. Understanding the removal mechanisms of PPCPs and
the influence of main technological parameters in anaerobic UASB and aerobic CAS
reactors[J]. Journal of Hazardous Materials. 2014, 278: 506-513.
[21] Kaya Y, Bacaksiz A M, Golebatmaz U, et al. Improving the performance of an aerobic
membrane bioreactor (MBR) treating pharmaceutical wastewater with powdered activated
carbon (PAC) addition[J]. Bioprocess and Biosystems Engineering. 2016, 39(4): 661-676.